EP1117484B1 - Multilayered shell catalysts for catalytic gaseous phase oxidation of aromatic hydrocarbons - Google Patents
Multilayered shell catalysts for catalytic gaseous phase oxidation of aromatic hydrocarbons Download PDFInfo
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- EP1117484B1 EP1117484B1 EP99944416A EP99944416A EP1117484B1 EP 1117484 B1 EP1117484 B1 EP 1117484B1 EP 99944416 A EP99944416 A EP 99944416A EP 99944416 A EP99944416 A EP 99944416A EP 1117484 B1 EP1117484 B1 EP 1117484B1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
- C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
- B01J37/0244—Coatings comprising several layers
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
- C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
- C07C51/313—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting with molecular oxygen
Definitions
- the invention relates to a coated catalyst for the catalytic gas-phase oxidation of aromatic hydrocarbons, containing a catalytically active composition with a content, based on the total amount of the catalytically active composition, of 1 to 40% by weight of vanadium oxide, calculated on an inert non-porous support as V 2 O 5, 60 to 99% by weight of titanium oxide, calculated as TiO 2 , up to 1% by weight of a cesium compound, calculated as Cs, up to 1% by weight of a phosphorus compound, calculated as P and up to a total content of 10% by weight of antimony oxide, calculated as Sb 2 O 3
- the invention further relates to a production process for these catalysts and a process for the production of carboxylic acids and / or carboxylic anhydrides and in particular phthalic anhydride using these catalysts.
- hot spots For temperature control are the tubes of a heat transfer medium, for example one Melted salt, surrounded. Despite this thermostatting, it can get in the catalyst bed to form so-called “hot spots” (hot spots) come in which there is a higher temperature than in the rest of the catalyst bed. These "hot spots” give rise to side reactions, such as the total combustion of the Starting material or they lead to the formation of undesirable, from The reaction product cannot be separated or can only be separated with a lot of effort By-products, for example for the formation of phthalide or Benzoic acid, in the manufacture of phthalic anhydride (PSA) from o-xylene.
- PSA phthalic anhydride
- the technology has started to differently active catalysts in layers to arrange the catalyst bed, usually the less active catalyst is arranged in the fixed bed so that the reaction gas mixture comes into contact with it first, i.e. it lies in the bed towards the gas inlet, whereas the more active catalyst for gas escape from the catalyst bed is located.
- the different active catalysts in the Catalyst bed can the reaction gas at the same temperature exposed, the two layers can be made differently active catalysts but also on different Reaction temperatures thermostatted with the reaction gas be brought into contact (DE-A 40 13 051).
- shell catalysts have proven themselves as catalysts for these oxidation reactions, in which the catalytically active mass is in the form of a shell on a carrier material which is generally inert under the reaction conditions, such as quartz (SiO 2 ), porcelain, magnesium oxide, tin dioxide, silicon carbide, rutile, alumina (Al 2 O 3 ), aluminum silicate, magnesium silicate (steatite), zirconium silicate or cerium silicate or mixtures of these carrier materials is applied.
- a carrier material which is generally inert under the reaction conditions
- quartz SiO 2
- porcelain porcelain
- magnesium oxide tin dioxide
- silicon carbide silicon carbide
- rutile rutile
- alumina Al 2 O 3
- aluminum silicate magnesium silicate
- steatite zirconium silicate or cerium silicate or mixtures of these carrier materials
- vanadium pentoxide is generally used as the catalytically active component of the catalytically active composition of these coated catalysts.
- the catalytically active composition can contain a large number of other oxidic compounds in small amounts which, as promoters, influence the activity and selectivity of the catalyst, for example by lowering or increasing its activity.
- promoters are the alkali metal oxides, in particular lithium, potassium, rubidium and cesium oxide, thallium (I) oxide, aluminum oxide, zirconium oxide, iron oxide, nickel oxide, cobalt oxide, manganese oxide, tin oxide, silver oxide, copper oxide, chromium oxide, molybdenum oxide, Tungsten oxide, iridium oxide, tantalum oxide, niobium oxide, arsenic oxide, antimony oxide, cerium oxide and phosphorus pentoxide called.
- the alkali metal oxides for example, act as promoters which reduce the activity and increase the selectivity, whereas oxidic phosphorus compounds, in particular phosphorus pentoxide, increase the activity of the catalyst but reduce its selectivity.
- the mash organic binder preferably copolymers, advantageous in the form of an aqueous dispersion of vinyl acetate / vinyl laurate, Vinyl acetate / acrylate, styrene / acrylate, vinyl acetate / maleate and also add vinyl acetate / ethylene, with binder amounts of 10-20% by weight, based on the solids content of the mash, were used (EP-A 744 214).
- the specified coating temperatures are the usable coating temperatures depending on the binder used between 50 and 450 ° C (DE 21 06 796).
- the applied binders burn after the Filling the catalyst into the reactor and starting up the Reactor within a short time.
- the binder additive also has the advantage that the active mass adheres well to the carrier, so that the transportation and filling of the catalyst are made easier.
- the gas composition not necessarily on the outer surface of the active material shell also the gas composition at inner points of the active mass equivalent. Rather, it is expected that concentration higher in primary oxidation products, the educt concentration in contrast, is lower than on the outer catalyst surface.
- This different gas composition should through a targeted adjustment of the active mass composition within the active mass shell to be taken into account to achieve optimal catalyst activity and selectivity.
- DE 22 12 964 already has a sequential method Spraying on mashes of various compositions and the use of the catalysts thus obtained for the production described by phthalic anhydride.
- the multilayer coated catalysts thus obtained result but still not satisfactory results and have the disadvantage that when used to oxidize o-xylene only unsatisfactory Yields of phthalic anhydride can be achieved.
- the object was therefore to produce multilayer coated catalysts which allow a further increase in the selectivity of the oxidation of aromatic hydrocarbons to carboxylic acids.
- This object was achieved by a coated catalyst for the catalytic gas-phase oxidation of aromatic hydrocarbons, containing a catalytically active composition with a content, based on the total amount of the catalytically active composition, of 1 to 40% by weight of vanadium oxide on an inert non-porous support , calculated as V 2 O 5 , 60 to 99% by weight of titanium oxide, calculated as TiO 2 , up to 1% by weight of a cesium compound, calculated as Cs, up to 1% by weight of a phosphorus compound, calculated as P and up to a total content of 10% by weight of antimony oxide, calculated as Sb 2 O 3 , which is characterized in that the catalytically active composition is applied in two or more than two layers, the inner layer or the inner layers having an antimony oxide content of 1 to 15 wt .-% and the outer
- the layer thickness of the inner layer or the sum of the layer thicknesses the inner layers are usually 0.02 to 0.2 mm, preferably 0.05 to 0.1 mm and the outer layer 0.02 to 0.2 mm, preferably 0.05 to 0.1 mm.
- the new catalysts preferably contain two concentric ones Layers of catalytically active mass, the inner layer preferably 2 to 10 and in particular 5 to 10% by weight of vanadium oxide and preferably 2 to 7, in particular 2.5 to 5% by weight of antimony oxide and the outer layer preferably 1 to 5, in particular 2 to 4 % By weight of vanadium oxide and preferably 0 to 2, in particular 0 to 1 Contains wt .-% antimony oxide.
- coated catalysts contain further constituents known per se for the oxidation of aromatic hydrocarbons to carboxylic acids, such as titanium dioxide in the anatase form with a BET surface area of 5 to 50 m 2 / g, preferably 13 to 28 m 2 / g.
- the non-porous carrier made of inert material consists, for. B. from quartz (SiO 2 ), porcelain, magnesium oxide, tin dioxide, silicon carbide, rutile, alumina (Al 2 O 3 ), aluminum silicate, magnesium silicate (steatite), zirconium silicate or cerium silicate or mixtures of these carrier materials.
- quartz SiO 2
- porcelain porcelain
- magnesium oxide titanium oxide
- tin dioxide silicon carbide
- rutile alumina
- Al 2 O 3 aluminum silicate
- magnesium silicate steatite
- zirconium silicate or cerium silicate or mixtures of these carrier materials consists, for. B. from quartz (SiO 2 ), porcelain, magnesium oxide, tin dioxide, silicon carbide, rutile, alumina (Al 2 O 3 ), aluminum silicate, magnesium silicate (steatite), zirconium silicate or cerium silicate or mixtures of these carrier materials.
- promoters examples include the alkali metal oxides, especially in addition to the above Cesium oxide, lithium, potassium and rubidium oxide, Thallium (I) oxide, aluminum oxide, zirconium oxide, iron oxide, nickel oxide, Cobalt oxide, manganese oxide, tin oxide, silver oxide, copper oxide, Chromium oxide, molybdenum oxide, tungsten oxide, iridium oxide, tantalum oxide, Niobium oxide, arsenic oxide, antimony oxide, cerium oxide called.
- Cesium oxide lithium, potassium and rubidium oxide
- Thallium (I) oxide aluminum oxide, zirconium oxide, iron oxide, nickel oxide, Cobalt oxide, manganese oxide, tin oxide, silver oxide, copper oxide, Chromium oxide, molybdenum oxide, tungsten oxide, iridium oxide, tantalum oxide, Niobium oxide, arsenic oxide, antimony oxide, cerium oxide called.
- the promoters mentioned also preferably come as additives the oxides of niobium, tungsten and lead in amounts from 0.01 to 0.50 wt .-%, based on the catalytically active mass, into consideration.
- Additive are mainly oxidic phosphorus compounds, especially phosphorus pentoxide.
- Sequential spraying is generally done as described in DE 22 12 964 and EP 21325, with the proviso that if possible chromatography effects, d. H. the emigration of individual components in the other layer can be avoided should. If the active components to be applied are not at least can sometimes exist as insoluble metal compounds it may be expedient to apply the thermal powder Undergo pretreatment, or in another way e.g. through additives to make them practically insoluble.
- the coating in the fluidized bed can be as described in DE 12 80 756 respectively.
- the method of powder coating which from WO-A 98/37967 and EP-A 714 700 is also known for sequential coating can be applied in several layers.
- the Solution and / or suspension of the catalytically active metal oxides, if necessary with the addition of auxiliaries, initially powder produced, one after the other, if necessary with an intermediate Heat treatment, shell-shaped applied to the carrier become.
- the catalyst is in usually, at least subsequently, subjected to a heat treatment.
- the new catalysts are generally suitable for the gas phase oxidation of aromatic C 6 to C 10 hydrocarbons, such as benzene, the xylenes, toluene, naphthalene or durol (1,2,4,5-tetramethylbenzene) to carboxylic acids and / or carboxylic acid anhydrides such as maleic anhydride, phthalic anhydride , Benzoic acid and / or pyromellitic dianhyride.
- aromatic C 6 to C 10 hydrocarbons such as benzene, the xylenes, toluene, naphthalene or durol (1,2,4,5-tetramethylbenzene)
- carboxylic acids and / or carboxylic acid anhydrides such as maleic anhydride, phthalic anhydride , Benzoic acid and / or pyromellitic dianhyride.
- the new shell catalysts make it possible significant increase in selectivity and yield in the Manufacture of phthalic anhydride.
- the catalysts prepared according to the invention are filled into reaction tubes thermostatted from the outside to the reaction temperature, for example by means of molten salt, and the reaction gas is prepared at the catalyst bed prepared in this way at temperatures of generally 300 to 450, preferably 320 to 420 and particularly preferably 340 to 420 400 ° C and at an overpressure of generally 0.1 to 2.5, preferably 0.3 to 1.5 bar with a space velocity of generally 750 to 5000 h -1 passed .
- the reaction gas supplied to the catalyst is generally produced by mixing a gas containing molecular oxygen, which in addition to oxygen may also contain suitable reaction moderators and / or diluents, such as steam, carbon dioxide and / or nitrogen, with the aromatic hydrocarbon to be oxidized, where the gas containing the molecular oxygen generally 1 to 100, preferably 2 to 50 and particularly preferably 10 to 30 mol% oxygen, 0 to 30, preferably 0 to 10 mol% water vapor and 0 to 50, preferably 0 to 1 mol% % Carbon dioxide, balance nitrogen.
- the molecular oxygen-containing gas is generally charged with 30 g to 150 g per Nm 3 of gas of the aromatic hydrocarbon to be oxidized.
- the gas phase oxidation is advantageously carried out in such a way that two or more zones, preferably two zones in the reaction tube located catalyst bed on different Reaction temperatures thermostatted, for example reactors with separate salt baths, as described in DE-A 22 01 528 or DE-A 28 30 765 are described, can be used.
- the gas entry of the Reaction gas located reaction zone which in general 30 to 80 mol% of the total catalyst volume comprises, to a by 1 to 20, preferably by 1 to 10 and in particular by 2 to 8 ° C higher reaction temperature than that at the gas outlet Reaction zone thermostated.
- the gas phase oxidation even without division into temperature zones for a single one Reaction temperature are carried out. Independent of Temperature structuring has proven to be particularly advantageous proven if in the above reaction zones Catalyst bed catalysts are used which are in their catalytic activity and / or chemical composition distinguish their active mass.
- Catalyst bed catalysts are used which are in their catalytic activity and / or chemical composition distinguish their active mass.
- two reaction zones in the first i.e. for the gas entry of the reaction gas reaction zone located
- a catalyst used the compared to the catalyst, which is in the second reaction zone, i.e. towards the gas outlet, has a slightly lower catalytic activity.
- the implementation is controlled by the temperature setting so that in the first zone most of that in the reaction gas contained aromatic hydrocarbon at maximum Yield is implemented.
- the anatase used contained: 0.18% by weight S, 0.08% by weight P, 0.24% by weight of Nb, 0.01% by weight of Na, 0.01% by weight of K, 0.004% by weight of Zr, 0.004 wt% Pb.
- Example 1 Preparation of the coated catalyst Ia - comparison
- the weight of the catalytically active composition applied in this way was 10.7% by weight, based on the total weight of the finished catalyst, after heat treatment at 400 ° C. for 1/2 h.
- the applied, catalytically active mass that is to say the catalyst shell, consisted of 0.40% by weight of cesium (calculated as Cs), 3.0% by weight of vanadium (calculated as V 2 O 5 ) and 96.6% by weight. % Titanium dioxide.
- the applied catalytically active composition consisted of 0.15% by weight of phosphorus (calculated as P), 7.5% by weight of vanadium (calculated as V 2 O 5 ), 3.2% by weight of antimony (calculated as Sb 2 O 3 ), 0.45% by weight of cesium (calculated as Cs) and 89.05% by weight of titanium dioxide.
- the catalytically active composition applied in this way i.e. the catalyst shell, consisted on average of 0.15% by weight of phosphorus (calculated as P), 7.5% by weight of vanadium (calculated as V 2 O 5 ), 3, 2% by weight of antimony (calculated as Sb 2 O 3 ), 0.4% by weight of cesium (calculated as Cs) and 89.05% by weight of titanium dioxide.
- Example 3 The procedure was as described in Example 3 with the proviso that initially 46 g of the powder described in Example 2 and then 47 g of the powder described in Example 1 on the Carrier were applied.
- Example 5 The procedure was as described in Example 5 with the modification that that the powder according to Example 2.61.5 g instead of 57.6 g vanadyl oxalate contained.
- Example 5 The procedure was as described in Example 5 with the modification that that the powder according to Example 2 20.02 g instead of 14.4 g antimony trioxide contained.
- Example 5 The procedure was as described in Example 5 with the modification that that the powder according to Example 2 9.0 g instead of 14.4 g of antimony oxide contained.
- precoated rings were then sprayed with a suspension of 400.0 g of anatase with a BET surface area of 20 m 2 / g, 30.7 g of vanadyl oxalate, 2.45 g of cesium sulfate, 618 g of water and 128 g of formamide until the weight the applied layer was 10.6% of the total weight of the finished catalyst.
- the catalytically active composition applied in this way that is to say the catalyst shell, consisted of 0.15% by weight of phosphorus (calculated as P), 7.5% by weight of vanadium (calculated as V 2 O 5 ), 3.2% by weight of antimony (calculated as Sb 2 O 3 ), 0.1% by weight of cesium (calculated as Cs) and 89.05% by weight of titanium dioxide.
- Example 11 Production of PSA - according to the invention and comparison
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Abstract
Description
Die Erfindung betrifft einen Schalenkatalysator für die katalytische
Gasphasenoxidation von aromatischen Kohlenwasserstoffen,
enthaltend auf einem inerten nicht-porösen Träger eine katalytisch
aktive Masse mit einem Gehalt, jeweils bezogen auf die
Gesamtmenge der katalytisch aktiven Masse, von 1 bis 40 Gew.-%
vanadiumoxid, berechnet als V2O5, 60 bis 99 Gew.-% Titanoxid, berechnet
als TiO2, bis zu 1 Gew.-% einer Cäsiumverbindung, berechnet
als Cs, bis zu 1 Gew.-% einer Phosphorverbindung, berechnet
als P und bis zu einem Gesamtgehalt von 10 Gew.-% Antimonoxid,
berechnet als Sb2O3
Weiterhin betrifft die Erfindung ein Herstellverfahren für diese
Katalysatoren und ein Verfahren zur Herstellung von Carbonsauren
und/oder Carbonsäureanhydriden und insbesondere von Phthalsäureanhydrid
unter Verwendung dieser Katalysatoren.The invention relates to a coated catalyst for the catalytic gas-phase oxidation of aromatic hydrocarbons, containing a catalytically active composition with a content, based on the total amount of the catalytically active composition, of 1 to 40% by weight of vanadium oxide, calculated on an inert non-porous support as V 2 O 5, 60 to 99% by weight of titanium oxide, calculated as TiO 2 , up to 1% by weight of a cesium compound, calculated as Cs, up to 1% by weight of a phosphorus compound, calculated as P and up to a total content of 10% by weight of antimony oxide, calculated as Sb 2 O 3
The invention further relates to a production process for these catalysts and a process for the production of carboxylic acids and / or carboxylic anhydrides and in particular phthalic anhydride using these catalysts.
Bekanntermaßen wird eine Vielzahl von Carbonsäuren und/oder Carbonsäureanhydriden technisch durch die katalytische Gasphasenoxidation von aromatischen Kohlenwasserstoffen, wie Benzol, den Xylolen, Naphthalin, Toluol oder Durol, in Festbettreaktoren, vorzugsweise Rohrbündelreaktoren, hergestellt. Dabei werden beispielsweise Benzoesäure, Maleinsäureanhydrid, Phthalsäureanhydrid, Isophthalsäure, Terephthalsäure oder Pyromellithsäureanhydrid gewonnen. Dazu wird im Allgemeinen ein Gemisch aus einem molekularen Sauerstoff enthaltenden Gas, beispielsweise Luft, und das zu oxidierende Ausgangsmaterial durch eine Vielzahl in einem Reaktor angeordneter Rohre geleitet, in denen sich eine Schüttung mindestens eines Katalysators befindet. Zur Temperaturregelung sind die Rohre von einem Wärmeträgermedium, beispielsweise einer Salzschmelze, umgeben. Trotz dieser Thermostatisierung kann es in der Katalysatorschüttung zur Ausbildung sogenannter "Heißer Flekken" (hot spots) kommen, in denen eine höhere Temperatur herrscht als im übrigen Teil der Katalysatorschüttung. Diese "hot spots" geben Anlaß zu Nebenreaktionen, wie der Totalverbrennung des Ausgangsmaterials oder sie führen zur Bildung unerwünschter, vom Reaktionsprodukt nicht oder nur mit viel Aufwand abtrennbarer Nebenprodukte, beispielsweise zur Bildung von Phthalid oder Benzoesäure, bei der Herstellung von Phthalsäureanhydrid (PSA) aus o-Xylol. Des Weiteren verhindert die Ausbildung eines ausgeprägten hot spots eine schnelles Hochfahren des Reaktors auf die Reaktionstemperatur der umsetzung, da ab einer bestimmten hot spot-Temperatur der Katalysator irreversibel geschädigt werden kann, so dass die Beladungserhöhung nur in kleinen Schritten durchführbar ist und sehr sorgfältig kontrolliert werden muß.It is known that a large number of carboxylic acids and / or Carboxylic anhydrides technically through the catalytic gas phase oxidation of aromatic hydrocarbons such as benzene Xylenes, naphthalene, toluene or durol, in fixed bed reactors, preferably tube bundle reactors. For example Benzoic acid, maleic anhydride, phthalic anhydride, Isophthalic acid, terephthalic acid or pyromellitic anhydride won. This is generally done using a mixture of one molecular oxygen-containing gas, for example air, and the starting material to be oxidized by a variety in one Reactor arranged pipes passed in which there is a bed at least one catalyst. For temperature control are the tubes of a heat transfer medium, for example one Melted salt, surrounded. Despite this thermostatting, it can get in the catalyst bed to form so-called "hot spots" (hot spots) come in which there is a higher temperature than in the rest of the catalyst bed. These "hot spots" give rise to side reactions, such as the total combustion of the Starting material or they lead to the formation of undesirable, from The reaction product cannot be separated or can only be separated with a lot of effort By-products, for example for the formation of phthalide or Benzoic acid, in the manufacture of phthalic anhydride (PSA) from o-xylene. Furthermore, the formation of a pronounced prevents hot spots a rapid startup of the reactor on the Reaction temperature of the implementation, as from a certain hot spot temperature the catalyst can be irreversibly damaged can, so the load increase only in small increments is feasible and must be checked very carefully.
Zur Abschwächung dieses hot spots wurde in der Technik dazu übergegangen, unterschiedlich aktive Katalysatoren schichtweise in der Katalysatorschüttung anzuordnen, wobei in der Regel der weniger aktive Katalysator so im Festbett angeordnet ist, dass das Reaktionsgasgemisch mit ihm als erstes in Kontakt kommt, d.h. er liegt in der Schüttung zum Gaseintritt hin, wohingegen der aktivere Katalysator zum Gasaustritt aus der Katalysatorschüttung hin gelegen ist. Die unterschiedlich aktiven Katalysatoren in der Katalysatorschüttung können bei der gleichen Temperatur dem Reaktionsgas ausgesetzt werden, es können die beiden Schichten aus unterschiedlich aktiven Katalysatoren aber auch auf unterschiedliche Reaktionstemperaturen thermostatisiert mit dem Reaktionsgas in Kontakt gebracht werden (DE-A 40 13 051).In order to weaken this hot spot, the technology has started to differently active catalysts in layers to arrange the catalyst bed, usually the less active catalyst is arranged in the fixed bed so that the reaction gas mixture comes into contact with it first, i.e. it lies in the bed towards the gas inlet, whereas the more active catalyst for gas escape from the catalyst bed is located. The different active catalysts in the Catalyst bed can the reaction gas at the same temperature exposed, the two layers can be made differently active catalysts but also on different Reaction temperatures thermostatted with the reaction gas be brought into contact (DE-A 40 13 051).
Als Katalysatoren haben sich für diese Oxidationsreaktionen sogenannte Schalenkatalysatoren bewährt, bei denen die katalytisch aktive Masse schalenförmig auf einem im Allgemeinen unter den Reaktionsbedingungen inerten Trägermaterial, wie Quarz (SiO2), Porzellan, Magnesiumoxid, Zinndioxid, Siliciumcarbid, Rutil, Tonerde (Al2O3), Aluminiumsilikat, Magnesiumsilikat (Steatit), Zirkoniumsilikat oder Cersilikat oder Mischungen dieser Trägermaterialien aufgebracht ist. Als katalytisch aktiver Bestandteil der katalytisch aktiven Masse dieser Schalenkatalysatoren dient im Allgemeinen neben Titandioxid in Form seiner Anatasmodifikation Vanadiumpentoxid. Des Weiteren können in der katalytisch aktiven Masse in geringen Mengen eine Vielzahl anderer oxidischer Verbindungen enthalten sein, die als Promotoren die Aktivität und Selektivität des Katalysators beeinflussen, beispielsweise in dem sie seine Aktivität absenken oder erhöhen. Als solche Promotoren seien beispielhaft die Alkalimetalloxide, insbesondere Lithium-, Kalium-, Rubidium- und Cäsiumoxid, Thallium-(I)-oxid, Aluminiumoxid, Zirkoniumoxid, Eisenoxid, Nickeloxid, Kobaltoxid, Manganoxid, Zinnoxid, Silberoxid, Kupferoxid, Chromoxid, Molybdänoxid, Wolframoxid, Iridiumoxid, Tantaloxid, Nioboxid, Arsenoxid, Antimonoxid, Ceroxid und Phosphorpentoxid genannt. Als die Aktivität vermindernder und die Selektivität erhöhender Promotor wirken z.B. die Alkalimetalloxide, wohingegen oxidische Phosphorverbindungen, insbesondere Phosphorpentoxid die Aktivität des Katalysators erhöhen, aber dessen Selektivität vermindern.So-called shell catalysts have proven themselves as catalysts for these oxidation reactions, in which the catalytically active mass is in the form of a shell on a carrier material which is generally inert under the reaction conditions, such as quartz (SiO 2 ), porcelain, magnesium oxide, tin dioxide, silicon carbide, rutile, alumina (Al 2 O 3 ), aluminum silicate, magnesium silicate (steatite), zirconium silicate or cerium silicate or mixtures of these carrier materials is applied. In addition to titanium dioxide in the form of its anatase modification, vanadium pentoxide is generally used as the catalytically active component of the catalytically active composition of these coated catalysts. In addition, the catalytically active composition can contain a large number of other oxidic compounds in small amounts which, as promoters, influence the activity and selectivity of the catalyst, for example by lowering or increasing its activity. Examples of such promoters are the alkali metal oxides, in particular lithium, potassium, rubidium and cesium oxide, thallium (I) oxide, aluminum oxide, zirconium oxide, iron oxide, nickel oxide, cobalt oxide, manganese oxide, tin oxide, silver oxide, copper oxide, chromium oxide, molybdenum oxide, Tungsten oxide, iridium oxide, tantalum oxide, niobium oxide, arsenic oxide, antimony oxide, cerium oxide and phosphorus pentoxide called. The alkali metal oxides, for example, act as promoters which reduce the activity and increase the selectivity, whereas oxidic phosphorus compounds, in particular phosphorus pentoxide, increase the activity of the catalyst but reduce its selectivity.
Zur Herstellung derartiger Schalenkatalysatoren wird nach den Verfahren von DE-A 16 42 938 und DE-A 17 69 998 eine wäßrige und/oder ein organisches Lösungsmittel enthaltende Lösung oder Suspension der Aktivmassenbestandteile und/oder deren Vorläuferverbindungen, welche im Folgenden als "Maische" bezeichnet wird, auf das Trägermaterial in einer beheizten Dragiertrommel bei erhöhter Temperatur aufgesprüht, bis der gewünschte Aktivmassenanteil am Katalysatorgesamtgewicht erreicht ist. Nach DE 21 06 796 läßt sich die Beschichtung auch in Wirbelbeschichtern durchführen, wie sie z.B. in der DE 12 80 756 angegeben sind. Beim Aufsprühen in der Dragiertrommel sowie beim Beschichten im Wirbelbett treten allerdings hohe Verluste auf, da erhebliche Mengen der Maische vernebelt bzw. durch Abrasion Teile der bereits aufbeschichteten Aktivmasse wieder abgerieben und durch das Abgas ausgetragen werden. Da der Aktivmasseanteil am Gesamtkatalysator im Allgemeinen nur eine geringe Abweichung vom Sollwert haben soll, da durch die Menge der aufgebrachten Aktivmasse und die Schichtdicke der Schale Aktivität und Selektivität des Katalysators stark beeinflußt werden, muß der Katalysator bei den geschilderten Herstellungsweisen häufig zur Bestimmung der aufgebrachten Aktivmassemenge abgekühlt, aus der Dragiertrommel bzw. der Wirbelschicht entnommen und nachgewogen werden. Wird zuviel Aktivmasse auf dem Katalysatorträger abgeschieden, ist im Allgemeinen eine nachträgliche, schonende Entfernung der zu viel aufgetragenen Aktivmassemenge ohne Beeinträchtigung der Festigkeit der Schale, insbesondere ohne Rissbildung in der Katalysatorschale, nicht möglich.For the production of such coated catalysts according to the Process of DE-A 16 42 938 and DE-A 17 69 998 an aqueous and / or a solution containing an organic solvent or Suspension of the active mass components and / or their precursor compounds, which is referred to below as "mash", onto the carrier material in a heated coating drum sprayed at an elevated temperature until the desired proportion of active mass of total catalyst weight is reached. According to DE 21 06 796 the coating can also be carried out in fluidized coaters, such as are specified in DE 12 80 756. At the Spray on in the coating drum and when coating in However, fluidized bed losses are high because of considerable losses Amounts of the mash are atomized or by parts of the abrasion already coated active composition rubbed again and by the Exhaust gas are discharged. Because the active mass share of the total catalyst generally only a small deviation from the setpoint should have, because of the amount of the applied active mass and the layer thickness of the shell activity and selectivity of the catalyst are strongly influenced, the catalyst in the described Manufacturing methods often used to determine the applied Active mass quantity cooled, from the coating drum or removed from the fluidized bed and weighed. Will be too much Active mass deposited on the catalyst support is generally a subsequent, gentle removal of too much applied Active mass quantity without impairing the strength the shell, especially without cracking in the catalyst shell, not possible.
Um diese Probleme abzumildern, wurde in der Technik dazu übergegangen, der Maische organische Binder, bevorzugt Copolymere, vorteilhaft in Form einer wäßrigen Dispersion, von Vinylacetat/Vinyllaurat, Vinylacetat/Acrylat, Styrol/Acrylat, Vinylacetat/Maleat sowie Vinylacetat/Ethylen zuzusetzen, wobei Bindermengen von 10-20 Gew.-%, bezogen auf den Feststoffgehalt der Maische, eingesetzt wurden (EP-A 744 214). Wird die Maische ohne organische Bindemittel auf den Träger aufgetragen, so sind Beschichtungstemperaturen über 150°C von Vorteil. Bei Zusatz oben angegebener Bindemittel liegen die brauchbaren Beschichtungstemperaturen je nach verwendetem Bindemittel zwischen 50 und 450°C (DE 21 06 796). Die aufgetragenen Bindemittel brennen nach dem Einfüllen des Katalysators in den Reaktor und Inbetriebnahme des Reaktors innerhalb kurzer Zeit aus. Der Binderzusatz hat zudem den Vorteil, dass die Aktivmasse gut auf dem Träger haftet, so dass Transport und Einfüllen des Katalysators erleichtert werden.To alleviate these problems, technology has been adopted to the mash organic binder, preferably copolymers, advantageous in the form of an aqueous dispersion of vinyl acetate / vinyl laurate, Vinyl acetate / acrylate, styrene / acrylate, vinyl acetate / maleate and also add vinyl acetate / ethylene, with binder amounts of 10-20% by weight, based on the solids content of the mash, were used (EP-A 744 214). Will the mash be without organic binders applied to the carrier, so are coating temperatures an advantage over 150 ° C. With addition above The specified coating temperatures are the usable coating temperatures depending on the binder used between 50 and 450 ° C (DE 21 06 796). The applied binders burn after the Filling the catalyst into the reactor and starting up the Reactor within a short time. The binder additive also has the advantage that the active mass adheres well to the carrier, so that the transportation and filling of the catalyst are made easier.
Gasphasenoxidationen an den oben geschilderten Schalenkatalysatoren finden nicht allein an der äußeren Oberfläche der Schale statt. Zur Erzielung einer für die vollständige Umsetzung der in technischen Verfahren angewandten hohen Beladungen des Reaktionsgases mit Edukt erforderlichen Katalysatoraktivität und -selektivität ist eine effiziente Nutzung der gesamten Aktivmassenschale des Katalysators und damit eine gute Zugänglichkeit des Reaktionsgases zu den in dieser Schale gelegenen Reaktionszentren notwendig. Da die Oxidation aromatischer Verbindungen zu Carbonsäuren und/oder Carbonsäureanhydriden über eine Vielzahl von Zwischenstufen vor sich geht und das Wertprodukt am Katalysator zu Kohlendioxid und Wasser weiteroxidiert werden kann, ist zur Erzielung eines hohen Umsatzes an Edukt unter gleichzeitiger Zurückdrängung des oxidativen Abbaus des Wertprodukts eine optimale Anpassung der Verweilzeit des Reaktionsgases in der Aktivmasse durch die Erzeugung einer geeigneten Aktivmassestruktur (beispielsweise deren Porosität und Porenradienverteilung) in der Katalysatorschale erforderlich.Gas phase oxidation on the shell catalysts described above do not find only on the outer surface of the bowl instead of. To achieve a full implementation of the in technical processes applied high loads of the reaction gas catalyst activity and selectivity required with starting material is an efficient use of the entire active mass shell of the catalyst and thus easy access to the reaction gas to the reaction centers in this bowl necessary. Because the oxidation of aromatic compounds to carboxylic acids and / or carboxylic anhydrides over a variety of Intermediate stages and the product of value on the catalyst can be further oxidized to carbon dioxide and water Achieving a high turnover of educt while pushing it back optimal oxidative degradation of the valuable product Adjustment of the residence time of the reaction gas in the active mass by creating a suitable active mass structure (for example their porosity and pore radius distribution) in the Catalytic converter shell required.
Des Weiteren ist zu berücksichtigen, dass die Gaszusammensetzung an der äußeren Oberfläche der Aktivmassenschale nicht zwangsläufig auch der Gaszusammensetzung an inneren Stellen der Aktivmasse entspricht. Vielmehr ist zu erwarten-, dass die Konzentration an primären Oxidationsprodukten höher, die Edukt-Konzentration dagegen niedriger ist, als an der äußeren Katalysatoroberfläche. Dieser unterschiedlichen Gaszusammensetzung sollte durch eine gezielte Einstellung der Aktivmassenzusammensetzung innerhalb der Aktivmassenschale Rechnung getragen werden, um zu einer optimalen Katalysatoraktivität und -selektivität zu gelangen. So ist in DE 22 12 964 bereits eine Methode der sequentiellen Aufsprühung von Maischen verschiedener Zusammensetzung und die Verwendung der so erhaltenen Katalysatoren für die Herstellung von Phthalsäureanhydrid beschrieben.It should also be borne in mind that the gas composition not necessarily on the outer surface of the active material shell also the gas composition at inner points of the active mass equivalent. Rather, it is expected that concentration higher in primary oxidation products, the educt concentration in contrast, is lower than on the outer catalyst surface. This different gas composition should through a targeted adjustment of the active mass composition within the active mass shell to be taken into account to achieve optimal catalyst activity and selectivity. DE 22 12 964 already has a sequential method Spraying on mashes of various compositions and the use of the catalysts thus obtained for the production described by phthalic anhydride.
Die so erhaltenen mehrschichtigen Schalenkatalysatoren ergeben aber noch keine befriedigenden Ergebnisse und haben den Nachteil, dass bei ihrer Verwendung zur Oxidation von o-Xylol nur unbefriedigende Ausbeuten an Phthalsäureanhydrid erzielt werden.The multilayer coated catalysts thus obtained result but still not satisfactory results and have the disadvantage that when used to oxidize o-xylene only unsatisfactory Yields of phthalic anhydride can be achieved.
Es bestand daher die Aufgabe, mehrschichtige Schalenkatalysatoren
herzustellen, die eine weitere Steigerung der Selektivität der
Oxidation von aromatischen Kohlenwasserstoffen zu Carbonsäuren
erlauben.
Diese Aufgabe wurde gelöst durch einen Schalenkatalysator für die
katalytische Gasphasenoxidation von aromatischen Kohlenwasserstoffen,
enthaltend auf einem inerten nicht-porösen Träger eine
katalytisch aktive Masse mit einem Gehalt, jeweils bezogen auf
die Gesamtmenge der katalytisch aktiven Masse, von 1 bis 40
Gew.-% Vanadiumoxid, berechnet als V2O5, 60 bis 99 Gew.-% Titanoxid,
berechnet als TiO2, bis zu 1 Gew.-% einer Cäsiumverbindung,
berechnet als Cs, bis zu 1 Gew.-% einer Phosphorverbindung,
berechnet als P und bis zu einem Gesamtgehalt von 10 Gew.-%
Antimonoxid, berechnet als Sb2O3, welches dadurch gekennzeichnet
ist, dass die katalytisch aktive Masse in zwei oder mehr als zwei
Schichten aufgebracht ist, wobei die innere Schicht oder die inneren
Schichten einen Antimonoxidgehalt von 1 bis 15 Gew.-% und
die äußere Schicht einen demgegenüber um 50 bis 100 % verringerten
Antimonoxidgehalt aufweisen und wobei die Menge der katalytisch
aktiven Masse der inneren Schicht oder der inneren Schichten
10 bis 90 Gew.-% der Menge der gesamten katalytisch aktiven
Masse beträgt.The object was therefore to produce multilayer coated catalysts which allow a further increase in the selectivity of the oxidation of aromatic hydrocarbons to carboxylic acids.
This object was achieved by a coated catalyst for the catalytic gas-phase oxidation of aromatic hydrocarbons, containing a catalytically active composition with a content, based on the total amount of the catalytically active composition, of 1 to 40% by weight of vanadium oxide on an inert non-porous support , calculated as V 2 O 5 , 60 to 99% by weight of titanium oxide, calculated as TiO 2 , up to 1% by weight of a cesium compound, calculated as Cs, up to 1% by weight of a phosphorus compound, calculated as P and up to a total content of 10% by weight of antimony oxide, calculated as Sb 2 O 3 , which is characterized in that the catalytically active composition is applied in two or more than two layers, the inner layer or the inner layers having an antimony oxide content of 1 to 15 wt .-% and the outer layer have a 50 to 100% reduced antimony oxide content and the amount of the catalytically active mass of the inner ski or the inner layers is 10 to 90% by weight of the amount of the total catalytically active composition.
Weiterhin wurde ein Herstellverfahren für diese Katalysatoren und ein Verfahren zur Herstellung von Carbonsäuren und/oder Carbonsäureanhydriden und insbesondere von Phthalsäureanhydrid unter Verwendung dieser Katalysatoren gefunden.Furthermore, a manufacturing process for these catalysts and a process for the production of carboxylic acids and / or carboxylic anhydrides and in particular of phthalic anhydride Found use of these catalysts.
Die Schichtdicke der inneren Schicht oder die Summe der Schichtdicken der inneren Schichten beträgt in der Regel 0,02 bis 0,2 mm, vorzugsweise 0,05 bis 0,1 mm und der äußeren Schicht 0,02 bis 0,2 mm, vorzugsweise 0,05 bis 0,1 mm.The layer thickness of the inner layer or the sum of the layer thicknesses the inner layers are usually 0.02 to 0.2 mm, preferably 0.05 to 0.1 mm and the outer layer 0.02 to 0.2 mm, preferably 0.05 to 0.1 mm.
Die neuen Katalysatoren enthalten bevorzugt zwei konzentrische Schichten aus katalytisch aktiver Masse, wobei die innere Schicht bevorzugt 2 bis 10 und insbesondere 5 bis 10 Gew.-% Vanadiumoxid und bevorzugt 2 bis 7, insbesondere 2,5 bis 5 Gew.-% Antimonoxid und die äußere Schicht bevorzugt 1 bis 5, insbesondere 2 bis 4 Gew.-% Vanadiumoxid und bevorzugt 0 bis 2, insbesondere 0 bis 1 Gew.-% Antimonoxid enthält.The new catalysts preferably contain two concentric ones Layers of catalytically active mass, the inner layer preferably 2 to 10 and in particular 5 to 10% by weight of vanadium oxide and preferably 2 to 7, in particular 2.5 to 5% by weight of antimony oxide and the outer layer preferably 1 to 5, in particular 2 to 4 % By weight of vanadium oxide and preferably 0 to 2, in particular 0 to 1 Contains wt .-% antimony oxide.
Darüberhinaus enthalten die Schalenkatalysatoren weitere an sich für die Oxidation von aromatischen Kohlenwasserstoffen zu Carbonsäuren bekannte Bestandteile wie Titandioxid in der Anatas-Form mit einer BET-Oberfläche von 5 bis 50 m2/g, vorzugsweise 13 bis 28 m2/g.In addition, the coated catalysts contain further constituents known per se for the oxidation of aromatic hydrocarbons to carboxylic acids, such as titanium dioxide in the anatase form with a BET surface area of 5 to 50 m 2 / g, preferably 13 to 28 m 2 / g.
Der nicht-poröse Träger aus inertem Material besteht z. B. aus Quarz (SiO2), Porzellan, Magnesiumoxid, Zinndioxid, Siliciumcarbid, Rutil, Tonerde (Al2O3), Aluminiumsilikat, Magnesiumsilikat (Steatit), Zirkoniumsilikat oder Cersilikat oder Mischungen dieser Trägermaterialien. Bevorzugt wird Steatit in Form von Kugeln mit einem Durchmesser von 3 bis 6 mm oder von Ringen mit einem äußeren Durchmesser von 5 bis 9 mm und einer Länge von 4 bis 7 mm verwendet.The non-porous carrier made of inert material consists, for. B. from quartz (SiO 2 ), porcelain, magnesium oxide, tin dioxide, silicon carbide, rutile, alumina (Al 2 O 3 ), aluminum silicate, magnesium silicate (steatite), zirconium silicate or cerium silicate or mixtures of these carrier materials. Steatite in the form of balls with a diameter of 3 to 6 mm or rings with an outer diameter of 5 to 9 mm and a length of 4 to 7 mm is preferably used.
Neben den bereits oben genannten fakultativen Zusätzen Cäsium und Phosphor können im Prinzip in der katalytisch aktiven Masse in geringen Mengen eine Vielzahl anderer oxidischer Verbindungen enthalten sein, die als Promotoren die Aktivität und Selektivität des Katalysators beeinflussen, beispielsweise indem sie seine Aktivität absenken oder erhöhen. Als solche Promotoren seien beispielhaft die Alkalimetalloxide, insbesondere außer dem genannten Cäsiumoxid, Lithium-, Kalium- und Rubidiumoxid, Thallium(I)oxid, Aluminiumoxid, Zirkoniumoxid, Eisenoxid, Nickeloxid, Kobaltoxid, Manganoxid, Zinnoxid, Silberoxid, Kupferoxid, Chromoxid, Molybdänoxid, Wolframoxid, Iridiumoxid, Tantaloxid, Nioboxid, Arsenoxid, Antimonoxid, Ceroxid genannt. In der Regel wird jedoch aus dieser Gruppe Cäsium als Promotor verwendet. Ferner kommen von den genannten Promotoren noch bevorzugt als Zusätze die Oxide von Niob, Wolfram und Blei in Mengen von 0,01 bis 0,50 Gew.-%, bezogen auf die katalytisch wirksame Masse, in Betracht. Als die Aktivität erhöhender aber die Selektivität vermindernder Zusatz kommen vor allem oxidische Phosphorverbindungen, insbesondere Phosphorpentoxid, in Betracht.In addition to the optional additives cesium and In principle, phosphorus can be found in the catalytically active mass small amounts of a variety of other oxidic compounds be included as promoters of activity and selectivity of the catalyst, for example, by its Reduce or increase activity. As such are promoters examples include the alkali metal oxides, especially in addition to the above Cesium oxide, lithium, potassium and rubidium oxide, Thallium (I) oxide, aluminum oxide, zirconium oxide, iron oxide, nickel oxide, Cobalt oxide, manganese oxide, tin oxide, silver oxide, copper oxide, Chromium oxide, molybdenum oxide, tungsten oxide, iridium oxide, tantalum oxide, Niobium oxide, arsenic oxide, antimony oxide, cerium oxide called. Usually however, cesium from this group is used as a promoter. In addition, the promoters mentioned also preferably come as additives the oxides of niobium, tungsten and lead in amounts from 0.01 to 0.50 wt .-%, based on the catalytically active mass, into consideration. As increasing the activity but reducing the selectivity Additive are mainly oxidic phosphorus compounds, especially phosphorus pentoxide.
Dabei ist in der Regel die innere Schicht des Katalysators phosphorhaltig und die äußere Schicht phosphorarm oder phosphorfrei.This is usually the inner layer of the catalyst containing phosphorus and the outer layer low in phosphorus or free of phosphorus.
Die Aufbringung der einzelnen Schichten des Schalenkatalysators
auf den inerten nicht-porösen Träger kann mit beliebigen an sich
bekannten Methoden erfolgen, z. B. durch
Das sequentielle Aufsprühen erfolgt im Allgemeinen wie in DE 22 12 964 und EP 21325 beschrieben, mit der Maßgabe, dass möglichst Chromatographie-Effekte, d. h. das Auswandern von einzelnen Bestandteilen in die andere Schicht vermieden werden sollte. Falls die aufzubringenden Aktiv-Komponenten nicht zumindest teilweise als unlösliche Metallverbindungen vorliegen, kann es dazu zweckmäßig sein, die aufzubringenden Pulver einer thermischen Vorbehandlung zu unterziehen, bzw. in anderer Weise z.B. durch Zusätze, praktisch unlöslich zu machen.Sequential spraying is generally done as described in DE 22 12 964 and EP 21325, with the proviso that if possible chromatography effects, d. H. the emigration of individual components in the other layer can be avoided should. If the active components to be applied are not at least can sometimes exist as insoluble metal compounds it may be expedient to apply the thermal powder Undergo pretreatment, or in another way e.g. through additives to make them practically insoluble.
Die Beschichtung im Wirbelbett kann wie in DE 12 80 756 beschrieben erfolgen. The coating in the fluidized bed can be as described in DE 12 80 756 respectively.
Die Methode der Pulverbeschichtung, die aus WO-A 98/37967 und EP-A 714 700 bekannt ist, kann auch für die sequentielle Beschichtung in mehreren Schichten angewandt werden. Dazu werden aus der Lösung und/oder Suspension der katalytisch aktiven Metalloxide, gegebenenfalls unter Zusatz von Hilfsmitteln, zunächst Pulver hergestellt, die nacheinander, gegebenenfalls mit zwischengeschalteter Wärmebehandlung, schalenförmig auf den Träger aufgebracht werden.The method of powder coating, which from WO-A 98/37967 and EP-A 714 700 is also known for sequential coating can be applied in several layers. To do this, the Solution and / or suspension of the catalytically active metal oxides, if necessary with the addition of auxiliaries, initially powder produced, one after the other, if necessary with an intermediate Heat treatment, shell-shaped applied to the carrier become.
Zur Entfernung flüchtiger Bestandteile wird der Katalysator in der Regel, zumindest anschließend, einer Wärmebehandlung unterzogen.To remove volatile components, the catalyst is in usually, at least subsequently, subjected to a heat treatment.
Die neuen Katalysatoren eignen sich generell zur Gasphasenoxidation aromatischer C6- bis C10-Kohlenwasserstoffe, wie Benzol, den Xylolen, Toluol, Naphthalin oder Durol (1,2,4,5-Tetramethylbenzol) zu Carbonsäuren und/oder Carbonsäureanhydriden wie Maleinsäureanhydrid, Phthalsäureanhydrid, Benzoesäure und/oder Pyromellithsäuredianhyrid.The new catalysts are generally suitable for the gas phase oxidation of aromatic C 6 to C 10 hydrocarbons, such as benzene, the xylenes, toluene, naphthalene or durol (1,2,4,5-tetramethylbenzene) to carboxylic acids and / or carboxylic acid anhydrides such as maleic anhydride, phthalic anhydride , Benzoic acid and / or pyromellitic dianhyride.
Insbesondere ermöglichen die neuen Schalenkatalysatoren eine signifikante Steigerung der Selektivität und Ausbeute bei der Herstellung von Phthalsäureanhydrid.In particular, the new shell catalysts make it possible significant increase in selectivity and yield in the Manufacture of phthalic anhydride.
Zu diesem Zweck werden die erfindungsgemäß hergestellten Katalysatoren in von außen auf die Reaktionstemperatur, beispielsweise mittels Salzschmelzen, thermostatisierte Reaktionsrohre gefüllt und über die so bereitete Katalysatorschüttung das Reaktionsgas bei Temperaturen von im Allgemeinen 300 bis 450, vorzugsweise von 320 bis 420 und besonders bevorzugt von 340 bis 400°C und bei einem Überdruck von im Allgemeinen 0,1 bis 2,5, vorzugsweise von 0,3 bis 1,5 bar mit einer Raumgeschwindigkeit von im Allgemeinen 750 bis 5000 h-1 geleitet.For this purpose, the catalysts prepared according to the invention are filled into reaction tubes thermostatted from the outside to the reaction temperature, for example by means of molten salt, and the reaction gas is prepared at the catalyst bed prepared in this way at temperatures of generally 300 to 450, preferably 320 to 420 and particularly preferably 340 to 420 400 ° C and at an overpressure of generally 0.1 to 2.5, preferably 0.3 to 1.5 bar with a space velocity of generally 750 to 5000 h -1 passed .
Das dem Katalysator zugeführte Reaktionsgas wird im Allgemeinen durch Vermischen von einem molekularen Sauerstoff enthaltenden Gas, das außer Sauerstoff noch geeignete Reaktionsmoderatoren und/oder Verdünnungsmittel, wie Dampf, Kohlendioxid und/oder Stickstoff, enthalten kann, mit dem zu oxidierenden, aromatischen Kohlenwasserstoff erzeugt, wobei das den molekularen Sauerstoff enthaltende Gas im Allgemeinen 1 bis 100 , vorzugsweise 2 bis 50 und besonders bevorzugt 10 bis 30 mol-% Sauerstoff, 0 bis 30, vorzugsweise 0 bis 10 mol-% Wasserdampf sowie 0 bis 50, vorzugsweise 0 bis 1 mol-% Kohlendioxid, Rest Stickstoff, enthalten kann. Zur Erzeugung des Reaktionsgases wird das molekularen Sauerstoff enthaltende Gas im Allgemeinen mit 30 g bis 150 g je Nm3 Gas des zu oxidierenden, aromatischen Kohlenwasserstoffs beschickt.The reaction gas supplied to the catalyst is generally produced by mixing a gas containing molecular oxygen, which in addition to oxygen may also contain suitable reaction moderators and / or diluents, such as steam, carbon dioxide and / or nitrogen, with the aromatic hydrocarbon to be oxidized, where the gas containing the molecular oxygen generally 1 to 100, preferably 2 to 50 and particularly preferably 10 to 30 mol% oxygen, 0 to 30, preferably 0 to 10 mol% water vapor and 0 to 50, preferably 0 to 1 mol% % Carbon dioxide, balance nitrogen. To generate the reaction gas, the molecular oxygen-containing gas is generally charged with 30 g to 150 g per Nm 3 of gas of the aromatic hydrocarbon to be oxidized.
Vorteilhaft wird die Gasphasenoxidation so durchgeführt, dass man zwei oder mehr Zonen, vorzugsweise zwei Zonen der im Reaktionsrohr befindlichen Katalysatorschüttung auf unterschiedliche Reaktionstemperaturen thermostatisiert, wozu beispielsweise Reaktoren mit getrennten Salzbädern, wie sie in DE-A 22 01 528 oder DE-A 28 30 765 beschrieben sind, eingesetzt werden können. Wird die Umsetzung in zwei Reaktionszonen durchgeführt, wie in DE-A 40 13 051 beschrieben, wird im Allgemeinen die zum Gaseintritt des Reaktionsgases hin gelegene Reaktionszone, welche im Allgemeinen 30 bis 80 mol-% des gesamten Katalysatorvolumens umfaßt, auf eine um 1 bis 20, vorzugsweise um 1 bis 10 und insbesondere um 2 bis 8°C höhere Reaktionstemperatur als die zum Gasaustritt hingelegene Reaktionszone thermostatisiert. Alternativ kann die Gasphasenoxidation auch ohne Aufteilung in Temperaturzonen bei einer einzigen Reaktionstemperatur durchgeführt werden. Unabhängig von der Temperaturstrukturierung hat es sich als besonders vorteilhaft erwiesen, wenn in den oben angegebenen Reaktionszonen der Katalysatorschüttung Katalysatoren eingesetzt werden, die sich in ihrer katalytischen Aktivität und/oder chemischen Zusammensetzung ihrer Aktivmasse unterscheiden. Vorzugsweise wird bei Anwendung zweier Reaktionszonen in der ersten, also zum Gaseintritt des Reaktionsgases hin gelegenen Reaktionszone, ein Katalysator eingesetzt, der in Vergleich zum Katalysator, welcher sich in der zweiten, also zum Gasaustritt hin gelegenen Reaktionszone, befindet, eine etwas geringere katalytische Aktivität hat. Im Allgemeinen wird die Umsetzung durch die Temperatureinstellung so gesteuert, dass in der ersten Zone der größte Teil des im Reaktionsgas enthaltenen aromatischen Kohlenwasserstoff bei maximaler Ausbeute umgesetzt wird.The gas phase oxidation is advantageously carried out in such a way that two or more zones, preferably two zones in the reaction tube located catalyst bed on different Reaction temperatures thermostatted, for example reactors with separate salt baths, as described in DE-A 22 01 528 or DE-A 28 30 765 are described, can be used. Becomes the reaction is carried out in two reaction zones, as in DE-A 40 13 051, the gas entry of the Reaction gas located reaction zone, which in general 30 to 80 mol% of the total catalyst volume comprises, to a by 1 to 20, preferably by 1 to 10 and in particular by 2 to 8 ° C higher reaction temperature than that at the gas outlet Reaction zone thermostated. Alternatively, the gas phase oxidation even without division into temperature zones for a single one Reaction temperature are carried out. Independent of Temperature structuring has proven to be particularly advantageous proven if in the above reaction zones Catalyst bed catalysts are used which are in their catalytic activity and / or chemical composition distinguish their active mass. Preferably when used two reaction zones in the first, i.e. for the gas entry of the reaction gas reaction zone located, a catalyst used, the compared to the catalyst, which is in the second reaction zone, i.e. towards the gas outlet, has a slightly lower catalytic activity. In general the implementation is controlled by the temperature setting so that in the first zone most of that in the reaction gas contained aromatic hydrocarbon at maximum Yield is implemented.
Wird die PSA-Herstellung mit den erfindungsgemäßen Katalysatoren unter Anwendung mehrerer Reaktionszonen, in denen sich unterschiedliche Katalysatoren befinden, durchgeführt, so können in allen Reaktionszonen die neuen Schalenkatalysatoren eingesetzt werden. Es können aber im Allgemeinen bereits erhebliche Vorteile gegenüber herkömmlichen Verfahren erzielt werden, wenn nur in einer der Reaktionszonen der Katalysatorschüttung, beispielsweise der ersten Reaktionszone, ein erfindungsgemäßer Schalenkatalysator verwendet wird und in den übrigen Reaktionszonen, beispielsweise der zweiten oder letzten Reaktionszone, auf herkömmliche Weise hergestellte Schalenkatalysatoren benutzt werden. Is the PSA production with the catalysts of the invention using several reaction zones in which different Catalysts are carried out, so can the new coated catalysts were used in all reaction zones become. However, there can already be significant benefits in general compared to conventional methods, if only in one of the reaction zones of the catalyst bed, for example the first reaction zone, a coated catalyst according to the invention is used and in the other reaction zones, for example the second or last reaction zone, to conventional ones Shell catalysts produced in this way can be used.
Der verwendete Anatas enthielt: 0,18 Gew.-% S, 0,08 Gew.-% P, 0,24 Gew.-% Nb, 0,01 Gew.-% Na, 0,01 Gew.-% K, 0,004 Gew.-% Zr, 0,004 Gew.-% Pb.The anatase used contained: 0.18% by weight S, 0.08% by weight P, 0.24% by weight of Nb, 0.01% by weight of Na, 0.01% by weight of K, 0.004% by weight of Zr, 0.004 wt% Pb.
Aus einer Suspension, bestehend aus 250,0 g Anatas, der eine BET-Oberfläche von 20 m2/g hatte, 13,6 g Vanadyloxalat (= 7,98 g V2O5), 1,37 g Cäsiumsulfat (= 1,01 g Cs), 940 g Wasser und 122 g Formamid wurden in einem Sprühtrockner bei einer Gaseintrittstemperatur von 280°C und einer Gasaustrittstemperatur des Trocknungsgases (Luft) von 120°C 270 g Pulver mit einer Partikelgröße von 3 bis 60 µm für 90 Gew.-% des Pulvers hergestellt. Nach Calcination des Pulvers (1 h bei 400°C) wurden 90 g des calcinierten Pulvers mit 10 g Melamin vermischt. 700 g Steatit (Magnesiumsilikat)-Ringe mit einem äußeren Durchmesser von 8 mm, einer Länge von 6 mm und einer Wandstärke von 1,5 mm wurden in einer Dragiertrommel bei 20°C während 20 Minuten mit 93 g des mit Melamin versetzten Pulvers unter Zusatz von 56 g eines 30 Gew.-% Wasser/70 Gew.-% Glycerin-Gemisches beschichtet. Anschließend wurde der so beschichtete Katalysatorträger bei 25°C getrocknet. Das Gewicht der so aufgetragenen katalytisch aktiven Masse betrug nach Wärmebehandlung bei 400°C für 1/2 h 10,7 Gew.-%, bezogen auf das Gesamtgewicht des fertigen Katalysators. Die aufgebrachte, katalytisch aktive Masse, also die Katalysatorschale, bestand aus 0,40 Gew.-% Cäsium (berechnet als Cs), 3,0 Gew.-% Vanadium (berechnet als V2O5) und 96,6 Gew.-% Titandioxid.From a suspension consisting of 250.0 g of anatase, which had a BET surface area of 20 m 2 / g, 13.6 g of vanadyl oxalate (= 7.98 g of V 2 O 5 ), 1.37 g of cesium sulfate (= 1 , 01 g Cs), 940 g water and 122 g formamide were in a spray dryer at a gas inlet temperature of 280 ° C and a gas outlet temperature of the drying gas (air) of 120 ° C 270 g powder with a particle size of 3 to 60 microns for 90 wt .-% of the powder produced. After calcination of the powder (1 h at 400 ° C.), 90 g of the calcined powder were mixed with 10 g of melamine. 700 g of steatite (magnesium silicate) rings with an outer diameter of 8 mm, a length of 6 mm and a wall thickness of 1.5 mm were added in a coating drum at 20 ° C. for 20 minutes with 93 g of the powder mixed with melamine coated by 56 g of a 30 wt .-% water / 70 wt .-% glycerol mixture. The catalyst support coated in this way was then dried at 25 ° C. The weight of the catalytically active composition applied in this way was 10.7% by weight, based on the total weight of the finished catalyst, after heat treatment at 400 ° C. for 1/2 h. The applied, catalytically active mass, that is to say the catalyst shell, consisted of 0.40% by weight of cesium (calculated as Cs), 3.0% by weight of vanadium (calculated as V 2 O 5 ) and 96.6% by weight. % Titanium dioxide.
Man verfuhr wie in Beispiel 1 beschrieben, verwendete jedoch eine Suspension, die aus 400,0 g Anatas, der eine BET-Oberfläche von 21 m2/g hatte, 57,6 g Vanadyloxalat (= 33,8 g V2O5), 2,75 g Cäsiumsulfat (= 2,02 g Cs), 14,4 g Antimontrioxid, 2,5 g Ammoniumdihydrogenphosphat (= 0,67 g P), 1500 g Wasser und 196 g Formamid bestand. Die aufgebrachte, katalytisch aktive Masse bestand aus 0,15 Gew.-% Phosphor (berechnet als P), 7,5 Gew.-% Vanadium (berechnet als V2O5), 3,2 Gew.-% Antimon (berechnet als Sb2O3), 0,45 Gew.-% Cäsium (berechnet als Cs) und 89,05 Gew.-% Titandioxid. The procedure was as described in Example 1, but using a suspension consisting of 400.0 g of anatase, which had a BET surface area of 21 m 2 / g, 57.6 g of vanadyl oxalate (= 33.8 g of V 2 O 5 ) , 2.75 g of cesium sulfate (= 2.02 g of Cs), 14.4 g of antimony trioxide, 2.5 g of ammonium dihydrogen phosphate (= 0.67 g of P), 1500 g of water and 196 g of formamide. The applied catalytically active composition consisted of 0.15% by weight of phosphorus (calculated as P), 7.5% by weight of vanadium (calculated as V 2 O 5 ), 3.2% by weight of antimony (calculated as Sb 2 O 3 ), 0.45% by weight of cesium (calculated as Cs) and 89.05% by weight of titanium dioxide.
Man verfuhr wie in den Beispielen 1 und 2 beschrieben mit der Abänderung, dass zunächst 46 g des unter 1 beschriebenen Pulvers und anschließend 47 g des unter 2 beschriebenen Pulvers auf den Träger aufgetragen wurden.The procedure was as described in Examples 1 and 2 with the modification that that initially 46 g of the powder described in 1 and then 47 g of the powder described in 2 on the Carrier were applied.
700 g Steatit (Magnesiumsilikat) Ringe mit einem äußeren Durchmesser von 8 mm, einer Länge von 6 mm und einer Wandstärke von 1,5 mm wurden in einer Dragiertrommel auf 160°C erhitzt und mit einer Suspension aus 400,0 g Anatas mit einer BET-Oberfläche von 20 m2/g, 57,6 g Vanadyloxalat (= 33,8 g V2O5), 14,4 g Antimontrioxid, 2,5 g Ammoniumdihydrogenphosphat (= 0,67 g P), 2,44 g Cäsiumsulfat (= 1,79 g Cs), 618 g Wasser und 128 g Formamid besprüht, bis das Gewicht der aufgetragenen Schicht 10,5 % des Gesamtgewichts des fertigen Katalysators betrug. Die auf diese Weise aufgebrachte katalytisch aktive Masse, also die Katalysatorschale, bestand im Mittel aus 0,15 Gew.-% Phosphor (berechnet als P), 7,5 Gew.-% Vanadium (berechnet als V2O5), 3,2 Gew.-% Antimon (berechnet als Sb2O3), 0,4 Gew.-% Cäsium (berechnet als Cs) und 89,05 Gew.-% Titandioxid.700 g of steatite (magnesium silicate) rings with an outer diameter of 8 mm, a length of 6 mm and a wall thickness of 1.5 mm were heated in a coating drum to 160 ° C. and with a suspension of 400.0 g of anatase with a BET -Surface area of 20 m 2 / g, 57.6 g of vanadyl oxalate (= 33.8 g of V 2 O 5 ), 14.4 g of antimony trioxide, 2.5 g of ammonium dihydrogen phosphate (= 0.67 g of P), 2.44 g Sprayed cesium sulfate (= 1.79 g Cs), 618 g water and 128 g formamide until the weight of the layer applied was 10.5% of the total weight of the finished catalyst. The catalytically active composition applied in this way, i.e. the catalyst shell, consisted on average of 0.15% by weight of phosphorus (calculated as P), 7.5% by weight of vanadium (calculated as V 2 O 5 ), 3, 2% by weight of antimony (calculated as Sb 2 O 3 ), 0.4% by weight of cesium (calculated as Cs) and 89.05% by weight of titanium dioxide.
Man verfuhr wie in Beispiel 3 beschrieben mit der Maßgabe, dass zunächst 46 g des in Beispiel 2 beschriebenen Pulvers und anschließend 47 g des im Beispiel 1 beschriebenen Pulvers auf den Träger aufgetragen wurden.The procedure was as described in Example 3 with the proviso that initially 46 g of the powder described in Example 2 and then 47 g of the powder described in Example 1 on the Carrier were applied.
Man verfuhr wie in Beispiel 5 beschrieben mit der Abänderung, dass das Pulver gemäß Beispiel 2.61,5 g statt 57,6 g Vanadyloxalat enthielt.The procedure was as described in Example 5 with the modification that that the powder according to Example 2.61.5 g instead of 57.6 g vanadyl oxalate contained.
Man verfuhr wie in Beispiel 5 beschrieben mit der Abänderung, dass das Pulver gemäß Beispiel 2 20,02 g statt 14,4 g Antimontrioxid enthielt. The procedure was as described in Example 5 with the modification that that the powder according to Example 2 20.02 g instead of 14.4 g antimony trioxide contained.
Man verfuhr wie in Beispiel 5 beschrieben mit der Abänderung, dass das Pulver gemäß Beispiel 2 9,0 g statt 14,4 g Antimonoxid enthielt.The procedure was as described in Example 5 with the modification that that the powder according to Example 2 9.0 g instead of 14.4 g of antimony oxide contained.
700 g Steatit-(Magnesiumsilikat)-Ringe mit einem äußeren Durchmesser von 8 mm, einer Länge von 6 mm und einer Wandstärke von 1,5 mm wurden in einer Dragiertrommel auf 160°C erhitzt und mit einer Suspension aus 400,0 g Anatas mit einer BET-Oberfläche von 20 m2/g, 57,6 g Vanadyloxalat (= 33,8 g V2O5), 14,4 g Antimontrioxid, 2,5 g Ammoniumdihydrogenphosphat (= 0,67 g P), 2.44 g Cäsiumsulfat (= 1,79 g Cs), 618 g Wasser und 128 g Formamid besprüht, bis das Gewicht der aufgetragenen Schicht 5.3 % des Gesamtgewichts des fertigen Katalysators betrug. Anschließend wurden diese vorbeschichteten Ringe mit einer Suspension aus 400,0 g Anatas mit einer BET-Oberfläche von 20 m2/g, 30,7 g Vanadyloxalat, 2,45 g Cäsiumsulfat, 618 g Wasser und 128 g Formamid besprüht, bis das Gewicht der aufgetragenen Schicht 10,6 % des Gesamtgewichts des fertigen Katalysators betrug.700 g of steatite (magnesium silicate) rings with an outer diameter of 8 mm, a length of 6 mm and a wall thickness of 1.5 mm were heated to 160 ° C. in a coating drum and mixed with a suspension of 400.0 g of anatase a BET surface area of 20 m 2 / g, 57.6 g vanadyl oxalate (= 33.8 g V 2 O 5 ), 14.4 g antimony trioxide, 2.5 g ammonium dihydrogen phosphate (= 0.67 g P), 2.44 g Sprayed cesium sulfate (= 1.79 g Cs), 618 g water and 128 g formamide until the weight of the layer applied was 5.3% of the total weight of the finished catalyst. These precoated rings were then sprayed with a suspension of 400.0 g of anatase with a BET surface area of 20 m 2 / g, 30.7 g of vanadyl oxalate, 2.45 g of cesium sulfate, 618 g of water and 128 g of formamide until the weight the applied layer was 10.6% of the total weight of the finished catalyst.
700 g Steatit-(Magnesiumsilikat)-Ringe mit einem äußeren Durchmesser
von 8 mm, einer Länge von 6 mm und einer Wandstärke von
1,5 mm wurden in einer Dragiertrommel auf 160°C erhitzt und mit
einer Suspension aus 400,0 g Anatas mit einer BET-Oberfläche von
20 m2/g, 57,6 g Vanadyloxalat, 14,4 g Antimontrioxid, 2,5 g Ammoniumdihydrogenphosphat,
0,61 g Cäsiumsulfat, 618 g Wasser und
128 g Formamid besprüht, bis das Gewicht der aufgetragenen
Schicht 10,5 % des Gesamtgewichts des fertigen Katalysators betrug.
Die auf diese Weise aufgebrachte katalytisch aktive Masse,
also die Katalysatorschale, bestand aus 0,15 Gew.-% Phosphor (berechnet
als P), 7,5 Gew.-% Vanadium (berechnet als V2O5),
3,2 Gew.-% Antimon (berechnet als Sb2O3), 0,1 Gew.-% Cäsium (berechnet
als Cs) und 89,05 Gew.-% Titandioxid.700 g of steatite (magnesium silicate) rings with an outer diameter of 8 mm, a length of 6 mm and a wall thickness of 1.5 mm were heated to 160 ° C. in a coating drum and mixed with a suspension of 400.0 g of anatase a BET surface area of 20 m 2 / g, 57.6 g of vanadyl oxalate, 14.4 g of antimony trioxide, 2.5 g of ammonium dihydrogen phosphate, 0.61 g of cesium sulfate, 618 g of water and 128 g of formamide were sprayed until the weight of the applied layer 10.5% of the total weight of the finished catalyst was. The catalytically active composition applied in this way, that is to say the catalyst shell, consisted of 0.15% by weight of phosphorus (calculated as P), 7.5% by weight of vanadium (calculated as V 2 O 5 ),
3.2% by weight of antimony (calculated as Sb 2 O 3 ), 0.1% by weight of cesium (calculated as Cs) and 89.05% by weight of titanium dioxide.
1,30 m des Katalysators III und anschließend jeweils 1,60 m der Katalysatoren Ia-Id bzw. IIa-IIe wurden in ein 3,85 m langes Eisenrohr mit einer lichten Weite von 25,2 mm eingefüllt. Das Eisenrohr war zur Temperaturregelung von einer Salzschmelze umgeben. Durch das Rohr wurden stündlich von oben nach unten 4,0 Nm3-Luft mit Beladungen an 98,5 gew.-%igem o-Xylol von 0 bis etwa 85 g/Nm3-Luft geleitet. Dabei wurden bei 75-85 g Beladung die in folgender Tabelle zusammengefaßten Ergebnisse erhalten (Ausbeute bedeutet das erhaltene PSA in Gewichtsprozent, bezogen auf 100 %-iges o-Xylol). 1.30 m of the catalyst III and then 1.60 m in each case of the catalysts Ia-Id and IIa-IIe were placed in a 3.85 m long iron pipe with a clear width of 25.2 mm. The iron pipe was surrounded by a salt melt for temperature control. 4.0 Nm 3 air with loads of 98.5% by weight o-xylene from 0 to about 85 g / Nm 3 air was passed through the tube from top to bottom every hour. The results summarized in the following table were obtained with a loading of 75-85 g (yield means the PSA obtained in percent by weight, based on 100% o-xylene).
Claims (12)
- A coated catalyst for the catalytic gas-phase oxidation of aromatic hydrocarbons, comprising, on an inert nonporous support, a catalytically active composition comprising, in each case based on the total amount of catalytically active composition, from 1 to 40% by weight of vanadium oxide, calculated as V2O5, from 60 to 99% by weight of titanium dioxide, calculated as TiO2, up to 1% by weight of a cesium compound, calculated as Cs, up to 1% by weight of a phosphorus compound, calculated as P, and a total of greater than 0 up to 10% by weight of antimony oxide, calculated as Sb2O3, wherein the catalytically active composition is applied in two or more layers, where the inner layer or inner layers have an antimony oxide content of from 1 to 15% by weight and the outer layer has, in contrast, an antimony oxide content which is from 50 to 100% lower, where the amount of catalytically active composition of the inner layer or the inner layers is from 10 to 90% by weight of the total amount of catalytically active composition, and where the proportions of constituents in the catalytically active composition are chosen from the given ranges such that they add up to 100% by weight.
- A coated catalyst as claimed in claim 1, wherein the catalytically active composition of the inner layer or the sum of the inner layers is from 30 to 70% by weight of the total amount of catalytically active composition of the catalyst.
- A coated catalyst as claimed in claim 1, wherein the thickness of the inner layer or the sum of the thicknesses of the inner layers is from 0.02 to 0.2 mm and the thickness of the outer layer is from 0.02 to 0.2 mm.
- A coated catalyst as claimed in claim 1, wherein the catalyst has two concentric layers of catalytically active composition, where the inner layer contains from 2 to 7% by weight of antimony oxide and the outer layer contains from 0 to 2% by weight of antimony oxide.
- A coated catalyst as claimed in claim 1, wherein the catalyst has two concentric layers of catalytically active composition, where the inner layer contains from 5 to 10% by weight of vanadium oxide and the outer layer contains from 1 to 5% by weight of vanadium oxide.
- A coated catalyst as claimed in claim 1, wherein the material of the inert nonporous support is steatite.
- A coated catalyst as claimed in claim 1, wherein the titanium oxide therein is present as titanium dioxide in the anatase form and has a BET surface area of from 13 to 28 m2/g.
- A coated catalyst as claimed in claim 1, wherein two concentric layers of catalytically active composition are applied in the form of a shell to an inert nonporous steatite support, where, apart from titanium dioxide in the anatase form having a BET surface area of from 13 to 28 m2/g, the inner layer comprises from 5 to 10% by weight of vanadium oxide, calculated as V2O5, and from 2 to 7% by weight of antimony oxide, calculated as Sb2O3, and the outer layer comprises from 1 to 5% by weight of vanadium oxide, calculated as V2O5, and from 0 to 2% by weight of antimony oxide, calculated as Sb2O3.
- A process for producing coated catalysts as claimed in claim 1, which comprises applying two or more than two layers of the catalytically active composition in succession to an inert nonporous support by spraying.
- A process for producing coated catalysts as claimed in claim 1, which comprises applying two or more than two layers of the catalytically active composition in succession to an inert nonporous support by coating with the binder-containing catalytically active composition in powder form.
- The use of catalysts as claimed in claim 1 for preparing carboxylic acids and/or carboxylic anhydrides by partial oxidation of aromatic hydrocarbons.
- A process for preparing phthalic anhydride by partial oxidation of o-xylene and/or naphthalene by means of gases comprising molecular oxygen, wherein a catalyst as claimed in any of claims 1 to 8 is used.
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US20030166972A1 (en) * | 2002-02-20 | 2003-09-04 | Regents Of The University Of California Office Of Technology Licensing | Process for production of formaldehyde from dimethyl ether |
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-
1998
- 1998-08-27 DE DE19839001A patent/DE19839001A1/en not_active Withdrawn
-
1999
- 1999-08-17 KR KR1020017002464A patent/KR100553285B1/en not_active IP Right Cessation
- 1999-08-17 AT AT99944416T patent/ATE238838T1/en not_active IP Right Cessation
- 1999-08-17 EP EP99944416A patent/EP1117484B1/en not_active Expired - Lifetime
- 1999-08-17 ID IDW20010476A patent/ID27448A/en unknown
- 1999-08-17 CN CN99810202A patent/CN1121907C/en not_active Expired - Fee Related
- 1999-08-17 WO PCT/EP1999/006012 patent/WO2000012214A1/en active IP Right Grant
- 1999-08-17 DE DE59905354T patent/DE59905354D1/en not_active Expired - Lifetime
- 1999-08-17 ES ES99944416T patent/ES2198952T3/en not_active Expired - Lifetime
- 1999-08-17 JP JP2000567305A patent/JP4571747B2/en not_active Expired - Fee Related
- 1999-08-17 US US09/763,661 patent/US6586361B1/en not_active Expired - Lifetime
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JP4571747B2 (en) | 2010-10-27 |
DE59905354D1 (en) | 2003-06-05 |
ID27448A (en) | 2001-04-12 |
ATE238838T1 (en) | 2003-05-15 |
JP2002523232A (en) | 2002-07-30 |
KR20010079692A (en) | 2001-08-22 |
WO2000012214A1 (en) | 2000-03-09 |
US6586361B1 (en) | 2003-07-01 |
CN1121907C (en) | 2003-09-24 |
EP1117484A1 (en) | 2001-07-25 |
KR100553285B1 (en) | 2006-02-22 |
ES2198952T3 (en) | 2004-02-01 |
CN1314827A (en) | 2001-09-26 |
DE19839001A1 (en) | 2000-03-02 |
TWI239868B (en) | 2005-09-21 |
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